Atomic Structure

EDUDIGM
Subatomic Particles
Basic Models
Wave Nature of Electromagnetic spectrum
Particle Nature of Electromagnetic spectrum
Dual Nature of Electromagnetic spectrum
Atomic Spectrum
Dual Nature of Matter
Heisenbergs Uncertainty Principle
Quantum Mechanical Model
Orbitals
Quantum Numbers
Filling of Orbitals
Electronic configuration
2
EDUDIGM
Proton (p+)
Located in the nucleus of the atom
Protons have a positive charge (+)
Much larger and heavier than electrons
Number of protons is different for each
element. If the number of protons changes,
the element changes.
Neutron (n
0
)
Located in the nucleus of the atom
Neutral particle (has no electrical charge)
A bit heavier than a proton
Electron (e-)
Found in a cloud outside the nucleus
Electrons have a negative charge (-)
Smallest particle
Orbit nucleus on energy levels
EDUDIGM
1. All matter is made of tiny indivisible particles
called atoms.
2. Atoms of the same element are identical. The
atoms of any one element are different from
those of any other element.
3. Atoms of different elements can combine with
one another in simple whole number ratios to
form compounds.

4. Chemical reactions occur when atoms are
separated, joined, or rearranged; however, atoms
of one element are not changed into atoms of
another by a chemical reaction.
Determined the charge to mass ratio for
electrons
Applied electric and magnetic fields to cathode
rays
Plum pudding model of the atom

It was first thought that protons and electrons were all mixed up.
Very much like a plum pudding. The negative electrons were like
the plums, randomly scattered in a positive dough of protons.
Negative electrons (like the plums)
Positive protons surround the
electrons, like the dough of the
pudding
Alpha particles
(positively charged
helium ions) from a
radioactive source
was directed toward
a very thin gold foil.
A fluorescent screen
was placed behind
the Au foil to detect
the scattering of
alpha (o) particles.
It was almost as incredible as of
you had fired a 15 inch shell at a
piece of tissue paper and it came
back and hit you!
I didnt expect
that!!
Most of the o-particles passed through the foil.
Many of the o-particles deflected at various
angles.
Surprisingly, a few particles were deflected
back from the Au foil.
Rutherford concluded that most of the mass of
an atom is concentrated in a core, called the
atomic nucleus.
The nucleus is positively charged.
Most of the volume of the atom is empty
space.
Rutherford Scattering
To explain results of the Rutherford scattering :

1) Atom must be mostly empty space

2) Positive charge must be concentrated in a small volume occupying a
very small fraction of the total volume of the atom
Christmas pudding model doesnt
work
Nuclear model does work
Atomic radius ~ 10
-10
m
Nuclear radius ~ 10
-14
m
Did not explain where the atoms negatively charged
electrons are located in the space surrounding its
positively charged nucleus.
We know oppositely charged particles attract each
other
What prevents the negative electrons from being
drawn into the positive nucleus?
Number of protons in each atom of
any element
All atoms want to balance their
protons and electrons to be
NEUTRAL (no electrical charge)
In a neutral atom, the # of protons =
the # of electrons
the sum of the mass of all the protons and
neutrons in an atom
-- measured in Atomic Mass Units (amu)

ATOMIC MASS
sum of protons and neutrons in the nucleus
can be used to find the number of neutrons in the
nucleus
Mass # = atomic # + n
Or
n = mass # - p

MASS NUMBER (A)

ATOMIC NUMBER
the number of (p+) and (e-)
(+) = (-)
ATOMIC MASS
(MASS NUMBER)
PROTONS (+) + NEUTRONS (0)
PROTONS AND NEUTRONS = NUCLEUS

The number of protons for a given atom
never changes.
The number of neutrons can change.
Two atoms with different numbers of
neutrons are called isotopes
Isotopes have the same atomic #
Isotopes have different atomic Mass #s
If an atom was the
size of a football
field. The nucleus
would be the size of
a gumdrop in the
center of the field.
The electrons would
be the size of a
small insect like a
fruit fly buzzing
around at lightning
speed in the region
of the bleachers.
The rest would be
empty space.
Dual Nature of Electromagnetic Radiation
Atomic Spectrum
23
EDUDIGM
To understand the electronic structure of atoms, one
must understand the nature of electromagnetic
radiation.

The distance between corresponding points on
adjacent waves is the wavelength ().
The number of waves passing
a given point per unit of time
is the frequency (v).
For waves traveling at the
same velocity, the longer the
wavelength, the smaller the
frequency.
The velocity of the wave is
given by the equation
c=v

All electromagnetic
radiation travels at
the same velocity:
the speed of light (c),
c = 3.00x10
8
m/s.

Note: Long wavelength
small frequency
Short wavelength
high frequency
increasing
wavelength
increasing
frequency
27
V.Montgomery & R.Smith
28
E
radiation
= Plancks constant x frequency of
radiation
E = hv
h = Plancks constant = 6.626 x 10
-34
J
s
When an object emits radiation, there must be
a minimum quantity of energy that can be
emitted at any given time.

29
Think of light as particles that each carry one
quantum of energy = photons
Photons: a particle of electromagnetic
radiation having zero mass and carrying a
quantum of energy
E
photon
= hv

30
E
photon
= hv
h = Plancks constant = 6.626 x 10
-34
J
s
c = v
c= speed of light = 3.00x10
8
m/s
v= (3.00x10
8
m/s)/(6.85x10-7m)
v=4.37x10
14
1/s
E
photon
= (6.626 x 10
-34
J
s)(4.37x10
14
1/s)
E
photon
= 2.90 x 10
-19
J

When light is incident on certain metallic surfaces,
electrons are emitted from the surface
This is called the photoelectric effect
The emitted electrons are called photoelectrons
The effect was first discovered by Hertz
The successful explanation of the effect was given by
Einstein in 1905
Received Nobel Prize in 1921 for paper on electromagnetic
radiation, of which the photoelectric effect was a part
The fact that light behaves like a wave under some
circumstances and like a particle under others
demonstrates that neither the wave model nor the
particle model alone is adequate for understanding the
behaviour of light. Both theories are correct. Very often
we refer to the wave-particle duality nature of light.
We apply either the wave model or the particle model,
depending on the phenomenon that requires an
explanation.

Emission spectra produced
when electron releases
energy and drops to a
lower orbit.

Absorption spectra
produced when electron
absorbed energy needed to
go to a higher orbit.

Energy levels constructed
based on spectral lines
observed for Hydrogen.

The Spectrum of Hydrogen
is like a very magnified view
of the electron energy
levels around the atom.

WAY COOL!!!!!!!!!!

Each element has it own
unique electron energy
levels with different
energy spacing between
each level.
Hydrogen always gives a set of line spectra
in the same position.
364.6
(nm)
H
o
H
|
H

H
o
H

656.3
486.1
434.1
410.2
Balmer found that the wavelength of these lines were
given accurately by the simple formula
,
1
2
1 1
2 2
|
.
|
\
|
=
n
R
where is the wavelength, R is a constant called the

Rydberg constant, and n may have the integral values 3,
4, 5, etc.* if is in meters,
1 7
10 097 . 1

= m R
Other series spectra for hydrogen have since been
discovered. These are known, after their discoveries,
as Lyman, Paschen, Brackett and Pfund series. The
formulas for these are
Lymann series:
, 4 , 3 , 2 ,
1
1
1 1
2 2
=
|
.
|
\
|
= n
n
R
Paschen series:
, 6 , 5 , 4 ,
1
3
1 1
2 2
=
|
.
|
\
|
= n
n
R
, 7 , 6 , 5 ,
1
4
1 1
2 2
=
|
.
|
\
|
= n
n
R
Brackett series:
, 8 , 7 , 6 ,
1
5
1 1
2 2
=
|
.
|
\
|
= n
n
R
Pfund series:
The Lyman series is in the ultraviolet, and the Paschen,
Brackett, and Pfund series are in the infrared. All these
formulas can be generalized into one formula which is
called the general Balmer series.
, 3 , 2 , 1 ,
1 1 1
2 2
+ + + =
|
.
|
\
|
= k k k n
n k
R
All the spectra of atomic hydrogen can be described

by this simple formula. As no one can explain this
formula, it was ever called Balmer formula puzzle.
Line Spectrum of hydrogen
Rydberg and Ritz subsequently obtained a more
general expression which applies to ALL hydrogen
spectral lines (not just visible), and also to certain
elements (eg alkaline metals):

|
|
.
|
\
|
=
2
1
2
2
1 1 1
n n
R
n
2
, n
1
integers, n
2
< n
1

R is called the Rydberg constant, which changes slightly from
element to element.
For hydrogen, R
H
= 1.097776 x 10
7
m
-1

We can use the emission spectrum to determine the
energy levels for the hydrogen atom.
Joseph Balmer (1885) first noticed that the
frequency of visible lines in the H atom spectrum
could be reproduced by:

v
1
2
2

1
n
2
n = 3, 4, 5, ..
The above equation predicts that as n increases,
the frequencies become more closely spaced.
Niels Bohr uses the emission spectrum of hydrogen
to develop a quantum model for H.
Central idea: electron circles the nucleus in
only certain allowed circular orbitals.
Bohr postulates that there is Coulombic attraction
between e- and nucleus. However, classical
physics is unable to explain why an H atom
doesnt simply collapse.
Bohr model for the H atom is capable of
reproducing the energy levels given by the
empirical formulas of Balmer and Rydberg.

E = 2.178x10
18
J
Z
2
n
2
|
\

|
.
|
Z = atomic number (1 for H)
n = integer (1, 2, .)
R
y
x h = -2.178 x 10
-18
J (!)

E = 2.178x10
18
J
Z
2
n
2
|
\

|
.
|
We can use the Bohr model to predict what AE is
for any two energy levels

AE = E
final
E
initial

AE = 2.178x10
18
J
1
n
final
2
|
\

|
.
|
|
(2.178x10
18
J)
1
n
initial
2
|
\

|
.
|

AE = 2.178x10
18
J
1
n
final
2

1
n
initial
2
|
\

|
.
|
|
The Bohr model can be extended to any single
electron system.must keep track of Z
(atomic number).
Examples: He
+
(Z = 2), Li
+2
(Z = 3), etc.
|
|
.
|
\
|
=

2
2
18
10 178 . 2
n
Z
J x E
The Bohr models successes are limited:
Doesnt work for multi-electron atoms.
The electron racetrack picture is incorrect.
That said, the Bohr model was a pioneering,
quantized picture of atomic energy levels.
r
Ze v m
e
0
2 2
8 2 tc
=
Kinetic energy (earlier slide)
r m
Ze
v
e 0
2
2
4tc
=
n
nh
mvr = =
t 2
quantisation of A.M. (last slide)
2 2
2 2
2
m r
n
v

=
2 2
2 2
0
2
4 m r
n
r m
Ze
e
=
tc
2
0
2 2
4
Ze m
n
r
e
tc
=
Bohr radius
So, introduction of the idea that angular momentum is quantised has
the desired effect: rn
2
. Simplifying the expression for r a bit (Z=1 for
hydrogen):
0
2
2
0
2 2
a n r
e m
h n
r
n
e
= =
t
c
a
0
, the radius of the n=1 orbit, is called the BOHR RADIUS
2
0
2
0
e m
h
a
e
t
c
=
We conclude that in the Bohr model only certain
orbital radii (and electron velocities) are allowed.
|
|
.
|
\
|
=
1 2 0
2
1 1
8 r r h
e
f
c t
|
|
.
|
\
|
=
2
1
2
2 0 0
2
1 1
8 n n a h
e
f
c t
|
|
.
|
\
|
=
2
1
2
2
2
0
3
4
1 1
8
n n
h
m e
f
e
c
|
|
.
|
\
|
=
2
1
2
2
1 1
n n
cR f
Rydberg-Ritz
R=1.07 x 10
7
m
-1

QUESTIONS ANSWERS
WHAT A simplified 2-D model of the atomic
structure to fill up the loopholes
that predecessors could not fulfill
WHY Rutherfords model couldnt answer
two important questions:
a) Stability of the atom
b) Explain the line spectra of atoms
So, Bohrs Chaalaki was to dump
Maxwell
QUESTIONS ANSWERS
WHERE APPLICABLE TO SINGLE ELECTRON SPECIES AHA!!
HOW 1. CONCEPT OF STATIONERY
STATES
2. mvr = nh/2

SPECIAL HIGHWAYS
LICENSE - CARS WITH A
CERTAIN FIXED PETROL TANK
CAPACITY TO BE ALLOWED
WITHOUT USING ANY
PETROL
3. Transition made from one
orbit to the other, energy will
be gained or lost equivalent
to the difference of the
energies of the two orbits in
the form of EMR
or quanta ( = )
PETROL CAPACITY OF THE
TANK OF THE CAR WILL
CHANGE AND THE EXCESS
PETROL WILL BE GIVEN OUT

ENERGY
VELOCITY
RADIUS

SPECTRAL LINES

n
nh
mvr = =
t 2
r
Ze v m
e
0
2 2
8 2 tc
=
|
|
.
|
\
|
=
2
1
2
2
1 1 1
n n
R
n
2
, n
1
integers, n
2
< n
1

Why do we get all the spectral lines when we analyze the
spectrum of H?
During a jump from state n
2
n
1
, what is the number of
spectral lines observed?
What is the probability of getting visible light when an electron jumps
from orbit 5 to orbit 1? Does this change for He+?
For a transition from a to b, the
5000, for a transition from n=6 to
n=b?
The spectral lines for the isotopes of H will be slightly different.
Why?

58
We know electrons behave as particles
In 1925, Louis de Broglie suggested that
electrons might also display wave properties
59
A free e- of mass (m) moving with a velocity (v)
should have an associated wavelength:
= h/mv
Linked particle properties (m and v) with a
wave property ()

5/28/2011
60
EDUDIGM
61
e- are detected by their interactions with
photons
Photons have about the same energy as e-
Any attempt to locate a specific e- with a
photon knocks the e- off its course
ALWAYS a basic uncertainty in trying to locate
an e-
62
Impossible to determine both the position
and the momentum of an e- in an atom
simultaneously with great certainty.

5/28/2011
63
EDUDIGM
64
An equation that treated electrons in atoms as
waves
Only waves of specific energies, and therefore
frequencies, provided solutions to the equation
Quantization of e- energies was a natural
outcome
65
Solutions are known as wave functions
Wave functions give ONLY the probability of
finding and e- at a given place around the
nucleus
e- not in neat orbits, but exist in regions called
orbitals
66
Here is the equation
Dont memorize this or write it down
It is a differential equation, and we need calculus to
solve it
-h (
2
)+ (
2
)+(
2
) +V =E
8()
2
m (x
2)
(y
2)
(z
2
)

Scary???

67
Probability likelihood
Orbital wave function; region in space where
the probability of finding an electron is high
Schrdingers Wave Equation states that
orbitals have quantized energies
But there are other characteristics to describe
orbitals besides energy
68
Definition: specify the properties of atomic
orbitals and the properties of electrons in
orbitals
There are four quantum numbers
The first three are results from Schrdingers
Wave Equation
69
Principal Quantum Number, n
Values of n = 1,2,3,
Positive integers only!
Indicates the main energy level occupied by the
electron
Describes the energy level, orbital size
As n increases, orbital size increases.

70
n = 1
n=2
n=3
n=4
n=5
n=6
Energy
71
More than one e- can have the same n value
These e- are said to be in the same e- shell
The total number of orbitals that exist in a
given shell = n
2
72
Angular momentum quantum number, l
Values of l = n-1, 0
Describes the orbital shape
Indicates the number of sublevel (subshells)
(except for the 1
st
main energy level, orbitals of
different shapes are known as sublevels or
subshells)
73
For a specific main energy level, the number of
orbital shapes possible is equal to n.
Values of l = n-1, 0
Ex. Orbital which n=2, can have one of two shapes
corresponding to l = 0 or l=1
Depending on its value of l, an orbital is
assigned a letter.

74
Angular magnetic quantum number, l
If l = 0, then the orbital is labeled s.
s is spherical.
75
If l = 1, then the orbital is labeled p.
dumbbell shape
76
If l = 2, the orbital is labeled d.
double dumbbell or four-leaf clover
77
If l = 3, then the orbital is labeled f.
78
n=1, only s orbitals
n=2, s and p orbitals
n=3, s, p, and d orbitals
n=4, s,p,d and f orbitals
Remember: l = n-1
79
Atomic Orbitals are designated by the principal
quantum number followed by letter of their
subshell
Ex. 1s = s orbital in 1
st
main energy level
Ex. 4d = d sublevel in 4
th
main energy level
80
Magnetic Quantum Number, m
l
Values of m
l
= +l0-l
Describes the orientation of the orbital
Atomic orbitals can have the same shape but
different orientations
81
s orbitals are spherical, only one orientation, so
m=0
p orbitals, 3-D orientation, so m= -1, 0 or 1 (x, y,
z)
d orbitals, 5 orientations, m= -2,-1, 0, 1 or 2

82
Electron Spin Quantum Number,m
s

Values of m
s
= +1/2 or 1/2
e- spin in only 1 or 2 directions
A single orbital can hold a maximum of 2 e-, which
must have opposite spins
QUESTIONS ANSWERS
WHAT Being not 100% sure is the answer
to all our problems.
A 3-D interpretation of an atom
taking us out of Newtons
deterministic world into the world of
uncertainty
WHY Bohr sucks.
Heisenberg, de-Broiglie,
Schrodingers Cat, Maxwell rock
QUESTIONS ANSWERS
WHERE APPLICABLE TO ALL THE SPECIES
HOW 1. From orbits to orbitals
2. Electrons as waves
3. Schrodingers equation
Schodingers Equation - BLACK BOX INPUT
OUTPUT
4
SOLUTIONS
Quantum
Numbers
Address to locate the location of Rajiv (which
makes a lot of sense)
Kolkata = Shell or Principal Quantum No.
Lake Town = Sub-shell or Azimuthal Quantum No.
Room = Orbital or Magnetic Quantum No.
Room can accommodate two people (M & F)
Highways =
Lanes =
Parking lot =
No. of cars in a parking lot =

Based on the relation between the four quantum numbers
(How?)
P.Q.No (n)
A.Q.No (l) 0 to n-1
M.Q.No (m) - +l to l including 0
S.Q.No (s) +1/2 or -1/2 for each value of l

Aufbau n+l rule

Hunds rule of maximum multiplicity

Paulis exclusion principle
Relation between &

.
+1 h/2
Cr (24) & Cu (29)
Config. of elements (n+l rule) nl
x
5/28/2011
90
EDUDIGM
91
Aufbau Principle: an e- occupies the lowest
energy orbital that can receive it.
Aufbau order:
92
No 2 e- in an atom can have the same set of
four quantum numbers (n, l, m
l,
m
s
).
Therefore, no atomic orbital can contain more
than 2 e-.

93
Hunds Rule: orbitals of equal energy are each
occupied by one e- before any orbital is
occupied by a second e-, and all e- in singly
occupied orbitals must have the same spin
94
Electron Configurations: arragenment of e- in
an atom
There is a distinct electron configuration for
each atom
There are 3 rules to writing electron
configurations:
95
The total of the superscripts must equal the
atomic number (number of electrons) of that
atom.
The last symbol listed is the symbol for the
differentiating electron.
96
The differentiating electron is the electron that is
added which makes the configuration different from
that of the preceding element.
The last electron.
H 1s
1

He 1s
2

Li 1s
2
, 2s
1

Be 1s
2
, 2s
2

B 1s
2
, 2s
2
, 2p
1

97
These diagrams are based on the electron
configuration.
In orbital diagrams:
Each orbital (the space in an atom that will hold a
pair of electrons) is shown.
The opposite spins of the electron pair is indicated.
98
1. Represent each electron by an arrow
2. The direction of the arrow represents the
electron spin
3. Draw an up arrow to show the first electron in
each orbital.
4. Hunds Rule: Distribute the electrons among
the orbitals within sublevels so as to give the
most unshared pairs.
Put one electron in each orbital of a sublevel before
the second electron appears.
Half filled sublevels are more stable than partially full
sublevels.
99
H |_
1s
Li |+ |_
1s 2s
B |+ |+ | __ __
1s 2s 2p
N |+ |+ | | |_
1s 2s 2p
100
When two atom collide, and a reaction takes place,
only the outer electrons interact.
These outer electrons are referred to as the valence
electrons.
Because of the overlaying of the sublevels in the larger
atoms, there are never more than eight valence
electrons.
101
Remember: the maximum number of valence
electrons is 8.
Only s and p sublevel electrons will ever be
valence electrons.
Put the dots that represent the s and p
electrons around the symbol.
Use the same rule (Hunds rule) as you fill the
designated orbitals.
102
Both dot diagrams and orbital diagrams will be use full
to use when we begin our study of atomic bonding.
We have been dealing with valence electrons since
our initial studies of the ions.
The number of valence electrons can be determined
by reading the column number.
Al = 3 valence electrons
Br = 7 valence electrons
All transitions metals have 2 valence electrons.
1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p
7s 5f 6d 7p
8s 5g 6f 7d 8p
2 2
8 10
8 18
18 36
18 54
32 86
32 118
? ?
N + 1 = n+l

Atomic Structure

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Atomic Structure

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EDUDIGM

where is the wavelength, R is a constant called the

All the spectra of atomic hydrogen can be described

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